JPH03137269A - Composition efficient in bleaching fiber and/or cellulose material at low temperature and bleaching method using same - Google Patents

Abstract

PURPOSE: To provide a bleaching composition effective for fibers and/or cellulosic materials at a low temperature, comprising peroxide, a water-soluble salt of a metal of atomic number of 25-29 and a metal ion blocking agent capable of forming a positively charged bleaching catalytic complex with the metal ion. CONSTITUTION: This bleaching composition comprises 85-100% peroxide, a bivalent water-soluble salt of metals of atomic numbers 25-29 and a ligand, and a contains 0.002-10% complex having a positive charge in an alkaline bath and a vacant coordinating position and 0-5% ligand type metallic ion blocking agent having a vacant coordinating position or capable of forming a positively charged complex, which can be converted into a chemical species having the vacant coordinating position in the bleaching bath, with the metal. The composition is used for bleaching fibers and/or cellulosic materials as a low-temperature alkaline bath.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to bleach compositions based on peroxides and valent metal complexes with atomic numbers 25-29.

BACKGROUND OF THE INVENTION The use of peroxides in linen cleaning compositions and other compositions for household or industrial use has been known for a long time. In fact, these peroxides are particularly useful for removing stains containing significant amounts of colored materials, such as coffee, tea, fruit, wine, cosmetics, and the like.

For this purpose, a wide range of peroxides are used, such as hydrogen peroxide, inorganic salts such as perborates, peroxycarbonates, persulfates, and perphosphates, and organic peroxycarphonic acids.

Among these compounds, those that generate hydrogen peroxide upon dissolution are very effective at high temperatures, but their effectiveness is greatly reduced at low temperatures. Therefore, they are not suitable for modern relatively low temperature domestic cleaning applications. Furthermore, if it is necessary to industrially work with this type of compound at high temperatures, it results in a high energy load, which affects the cost.

To solve this problem, organic compounds with e.g. ester and/or amide bonds are added to peroxide bleach compositions to generate peroxyacids and improve bleaching efficiency at low temperatures. is proposed. However, in order for these compounds known in the art as bleach activators to be effective, they must be added in relatively large amounts. Therefore, product costs are increased and bleach activation may interfere with the action of other ingredients in the composition.

In fact, not all of the peroxide in the bleach composition used is effectively used to oxidize the colorants that make up the soil. In fact, some of the peroxide decomposes into the corresponding anion and gaseous oxygen, which does not participate in bleaching, and this decomposition results in the loss of a considerable amount of the expensive material peroxide.

It has long been known that heavy metals contained as impurities in wash water act as catalysts in the decomposition of peroxides. To avoid this effect, strong sequestering agents such as ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA), among others, may be added to the bleach composition to reduce free heavy metal salts. It has been proposed to reduce peroxide decomposition and thereby stabilize peroxide.

The prior art also describes solutions that go beyond stabilizing peroxides against the catalytic action of their decomposition by heavy metals and attempt to control that catalytic action, which is reflected in an increased bleaching activity. has been done.

Furthermore, European Patent Specification Nos. 82563 and 1
No. 11,964, when manganese is used as a bleaching catalyst, substances that dissolve to generate carbonate anions are added, or a mixture of orthophosphoric acid and condensed phosphoric acid, which also acts as a cleaning enhancer, is added. It is also proposed that

U.S. Pat. No. 4,620,935 also describes the use of manganese ions and the retention of a low concentration of Ca"" ions in the wash water to promote the catalytic action of manganese. Ill.

Another solution to the above problem is to adjust the amount of dissolved free metal to achieve an optimal balance between oxidation activity and peroxide decomposition.

To this end, British Patent No. 984,459 introduces divalent copper into bleach compositions with a formation constant between 101' and 1015 as a solution to high-temperature cleaning. When added with an excess amount of sequestering agent to form a complex with a formation constant, the amount of dissolved free metal is reduced to 10-6.
It is maintained at ~10-5 mol. According to the British patent specification, this concentration is said to be the optimum concentration for obtaining the best bleaching efficiency. A sequestering agent that gives a formation constant lower than 1011 liberates an excess amount of free metal, thereby causing rapid decomposition of the peroxide. On the other hand, if the generation constant is 10
Sequestering agents that give complexes greater than '5 are said to excessively deplete the free metal in solution, thereby reducing bleach activity.

Another alternative solution is European Patent Application No. 72,
No. 166 discloses the sequestration of heavy metals with high catalytic activity for the decomposition of peroxides, together with auxiliary metals of low catalytic activity, which in combination with these metals give complexes with formation constants exceeding 1015. It is proposed to be used in the presence of agents.

To improve the efficiency of peroxide bleaches, U.S. Pat. On the other hand, if this metal is present in a free form sufficiently to be absorbed by the cloth, etc., once it is present on the cloth, etc., it will promote the decomposition of the peroxide in that area and have a good effect. It is proposed to give high bleaching efficiency.

Complexing agents must be kept in check to maintain low concentrations of dissolved free metals to avoid high decomposition, while overly strong sequestering agents may prevent absorption of free metals into the fabric and It must be determined in consideration of reducing activity. This patent describes aminocarboxylic acids in which the nitrogen atom is separated from the carboxyl group by up to two carbon atoms as capping agents and as the most suitable capping agents.

The currently employed complexing agents generally have a negative charge at the pH value during the washing and bleaching process, and therefore the complexes formed in combination with divalent metals are neutral or slightly negatively charged. There is.

[Problem to be Solved by the Invention] Certain complexes of divalent metals having a net positive charge at normal alkaline pH values during bleaching processes are particularly effective in peroxide bleaching at low temperatures. was discovered.

These complexes do not act to control the amount of free metal and thus effectively catalyze decomposition, but they do themselves catalyze decomposition on the substrate to be bleached; Provides superior low temperature bleaching efficiency than that obtained with free metal assisted catalysis.

The object of the present invention is therefore to provide a method based on peroxides and bleach catalysts capable of enhancing the action of peroxides at low temperatures.
The object of the present invention is to provide a bleach composition for fibers or cellulosic materials that is effective at low temperatures even in the absence of so-called "bleach activators" or "peracid precursors."

[Means for Solving the Problems] More specifically, the present invention provides peroxides having an atomic number of 25 to 25.
29 and a ligand-type sequestering agent which together with said divalent metal form a net positively charged bleach catalyst complex in an aqueous medium when the bleach bath has an alkaline pH value. It relates to a bleaching agent composition for fibers and/or cellulosic materials that is efficient at low temperatures and is characterized by containing the following.

At normal pH values in these bleaching processes, positively charged metal complexes either have vacant coordination sites or are converted into positively charged complex species with such vacant coordination sites in the washing bath. It is subject to change.

These vacant coordination sites are important for the species to catalyze peroxide decomposition.

Suitable Ligands for Producing the Bleach Compositions of the Invention"
It is a di-or polydentate compound that can form complexes with a net positive charge with divalent metals at alkaline pH. Although not wishing to be limited thereto, the excellent effects obtained by the composition of the present invention include:
This appears to be due to the tendency of positively charged structures to be adsorbed onto textiles or cellulosic fibers.

It has been shown that ligands capable of forming complexes with divalent copper with an overall formation constant higher than 1015 are particularly recommended for producing the complexes that are the subject of the present invention.

In particular, diamines are suitable as the ligands forming the catalyst according to the present invention. The nitrogen atoms contained in the diamine are separated by buttons having up to 5 atoms, and they may be optionally substituted. The substituent is
It may be a functional group with the aid of which it additionally chelates with the divalent metal to form a complex, or it may not undergo such chelation.

As a guideline, the following may be exemplified as a sequestering agent that satisfies the above conditions.

Ligand Formation constant with divalent copper: 1.2-cyclohexyldiamine
10151.2-ethylenediamine 3.2X10'
91.3-Propylenediamine
1.6X10” 1.2-propylene diamine
1.3X10” diethylenetriamine 2.5X10”
22'-bipyridine
1.3X10171.4, 8.11-tetraase-2,
3,9,10-tetramethylcyclotetradecane-1,
3,8,ICl-1,0'' Tetraene According to one embodiment of the present invention, the bleach composition comprises the following components as essential components, wherein the molar ratio of ligand to metal ion is from 0.5 to 100. Salts of metal divalent cations with atomic numbers 25 to 29 having the composition 0001 to
5% (calculated as cation weight) of positively charged complexes that have vacant coordination sites or that can be converted into a type having such vacant coordination sites in the bleach bath. Ligands that can be formed with 0.001-10%, and monoperoxides 80-100%.

When using the composition of the present invention in the bleaching process, the usual amount used is 1 g/j2-10 g/u, and the bleach catalyst concentration in the washing bath is 0.1-50 ppm as metal.
, preferably 1 to 20 ppm.

The amount of ligand is set depending on the amount of metal used, and is set so that the molar ratio of ligand/metal falls within the range of about 0.5 to 100.

The composition can be constituted by a precursor of the catalyst complex. That is, soluble salts of metal cations with atomic numbers from 25 to 29, ligands and peroxides which in combination with the metal cations form complexes with a net positive charge under alkaline conditions. Alternatively, these catalyst precursors may already be combined as a composition forming the catalyst complex.

2 These components may be added separately to the bleach bath and the required catalyst complexes formed in this bath. In this embodiment, the ligand must be added to the wash bath first, followed by the metal. This is because the uncomplexed metal
This is because peroxides present in the bath are decomposed.

The bleach compositions of the present invention may be used as bleach additives in final detergent compositions.

The invention also relates to a bleaching process, characterized in that the bleach composition according to the invention is added to a washing bath.

[Example] Without limiting the scope of the present invention, by way of example, EMP
The results are shown as percent soil removal when cleaning a 5 x 5 cm sample of A-114 with the bleach composition of the present invention.

EMPA-114 here means a standard cotton fabric stained with red wine according to the Swiss Materials Testing Association standard.

To determine the stain removal rate, reflectance of the clean fabric (
Ri), the reflectance of the dirty cloth before washing (Rh) and -
Measure the reflectance (Rr) of the cloth after washing.

Reflectance measurement was performed using Carl Zeiss Elrefo (Elr
epho) test machine with xenon lamp, FL40 and FL46 (UV screen and ]0 filter)
It was used with

The percent dirt removal rate is calculated by the following formula: D=(Rr-Rb)/(Ri-Rb)xlOO(Rr,
, Rh and Ri are as above, D is dirt removal rate (%)
).

To facilitate the designation of the complexes used in these examples, the following abbreviations will be used for the ligands that form part of the complexes.

Ligand Abbreviation 1.2-cyclohexyldiamine
CHDl, 2-ethylenediamine
enl, 2-propylenediamine prop diethylenetriamine
dienl, 4,8.11-tetraase-2,3,
9,10-tetramethylcyclotetradecane-1,3,
8,10-TTCT Tetraene As mentioned above, the compounds involved in the compositions of the present invention are:
In combination they form a complete bleach composition to be added to the cleaning bath. However, to facilitate comparisons between cleanings with different catalysts, the tests described below involve splitting a single bleach solution using sodium perborate-hydrate and adding different catalysts to the aliquots. The test was carried out by adding .

That is, prior to the test, a solution of 13 g of sodium perborate hydrate in 10,000 cc of deionized water was prepared, and 1,000 cc of the solution was taken at 30° C. while stirring at 225 rpm with a mechanical stirrer. Hold.

A 5 x 5 cm piece of EMPA-1145 semi-soiled cloth is added to the above solution along with the amount of pre-prepared complex shown in the following table.

[M] Workshop 16 (2) Work No. Contains scrap Ligand 2 Cu” -1-2ppm
03 Cu” prop 6p
pm 24 Cu” di
en 3ppm 15C
u”CHD O19ppm
26 Cu” TTCT 2ppm
17 Cu”en
4.3ppm 28 Ni”
en 6ppm 3
9 Mn” en O, 5pp
m 10010 Mn”en
0.5ppm 10 In the above table, [
M] is the metal ion concentration in the cleaning bath, [L] /
[M] represents the ratio of the molar concentration of the ligand to the molar concentration of the metal cation in the bath.

After 30 minutes, 60 minutes, and 90 minutes, take out two fabric samples, rinse them in water, dry them, measure the reflection value Rr, and enter the results into the above formula to calculate the percent dirt. Find the removal rate. The table below shows the stain removal rate results for each composition number.

No. 1 3B, 4 2 35.3 3 50.8 4 54.4 5 38.1 6 30.2 7 57.1 8 40.2 9 65.0 10 54.0 Tan Risa 45.6 53.2 43.8 50.8 77.3 90.3 79.2 87.9 60.1 80.1 42.3 63.7 90.3 98.5 51.4 62.8 75.8 78.9 77.0 90.9 The attached Figures 1, 2 and 3 show the stain removal rate results after 30 minutes, 60 minutes and 90 minutes, respectively, in each bleach composition. This is reproduced in a graph.

[Effects of the Invention] Looking at these graphs, when fabrics are bleached using the composition containing the catalyst of the present invention, the upper y- of the white melon is clearly observed.

[Brief explanation of the drawing]

Figures 1, 2 and 3 show the percent soil after 30 minutes, 60 minutes and 90 minutes, respectively, of bleaching standard stained fabric pieces using compositions of the invention and comparative compositions. It is a graph which shows the measurement result of a removal rate. 30 go low mouth Cu

Claims (1)

[Scope of Claims] 1. Peroxide, a soluble salt of a divalent metal having an atomic number of 25 to 29, and said divalent metal together in an aqueous medium have a net positive effect when the bleaching bath has an alkaline pH value. 1. A low-temperature, efficient bleaching composition for fibers and/or cellulosic materials, characterized in that it contains a ligand-type sequestering agent which forms a charged bleaching catalyst complex. 2. Claim 1, characterized in that the positively charged bleach catalyst complex has free coordination sites or can be transformed into a species with such free coordination sites in the bleach bath. The bleach composition described in . 3. Claim 1 or 2, characterized in that the ligand contained in the catalyst complex is a ligand that forms a complex with divalent copper ion having a formation constant of greater than 10^1^5. The bleach composition described. 4. Claim 3, wherein the ligand is a diamine, and the diamine is characterized in that its nitrogen atoms are separated by 5 or less atoms, and may optionally be substituted with a functional group. The bleach composition described in . 5. According to any one of claims 1 to 4, characterized in that the quantitative ratio of the ligand to the divalent metal used is between about 0.5 and 100 in terms of ligand/metal molar ratio. bleach composition. 6. Contains the following essential components and is characterized in that the molar ratio of the ligand to the metal ion is 0.5 to 100.
Bleach composition according to any one of claims 1 to 5: - 0.001 salt of a divalent metal ion having an atomic number of 25 to 29.
~5% (based on cation weight), - forms positively charged complexes with metals that have vacant coordination sites or that can be transformed into species with such vacant coordination sites in the bleach bath; Possible ligand 0.
001-10%, and - peroxide 80-100%. 7. Claim 1 characterized by containing the following ingredients:
The bleach composition according to any one of items 6 to 6: - a complex of a divalent cation of a metal having an atomic number of 25 to 29 and a ligand, which has a net positive charge at an alkaline pH, and has a vacancy. A complex with a coordination site of 0.
002-10%, - coordination capable of forming with the metal a positively charged complex that has vacant coordination sites or that can be transformed into a species with such vacant coordination sites in the bleach bath; Child 0~
5% excess, and - 85-100% peroxide. 8. A method for bleaching fibers or cellulosic materials, which comprises using the bleach composition according to any one of claims 1 to 7.